Disazo dyestuffs and process of making same



Patented Nov. 26, 1946 DISAZO DYESTUFFS AND PROCESS OF MAKING SAME Walter Anderau, Basel, Switzerland, assignor to Society of Chemical Industry in Basle, Basel, Switzerland, a Swiss company No Drawing. Application August 2, 1943, Serial No. 497,077. In Switzerland August 21, 1942 18 Claims.

A relatively small number of dyestuffs are already known which contain B-hydroxyquinoline or its substitution products as a component. However, as far as monoand disazo-dyestuffs are concerned, these dyestufis are intended for dyeing wool or other animal fibers or varnishes and plastic masses if devoid of solubilizing groups. Recently it has also become known to make use of 8-hydroxyquinolines for the manufacture of substantive dyes, i. e. dyestuffs possessin aflinity for vegetable fibers, such as cotton, linen or rayon from regenerated cellulose. It has been said however that only trisand polyazo-dyestufifs are sufiiciently substantive. Furthermore clear red shades have not been obtained with the known substantive dyestuffs containing S-hydroxyquinolines as components.

It is an object of the present invention to provid a series of new valuable dyestufis containing only two azo groups and an 8-hydroxyquinoline as component, which are perfectly substantive. It is a further object of the present invention to provide dyestuifs capable of forming complex metal compounds. More particularly the present invention provides dyestuffs which are perfectly soluble in the form of their normal alkali metal salts, but become substantially insoluble on conversion into complex metal compounds, especially copper compounds, the said conversion being preferably carried out in the dyebath as described below. Still more particularly it is an object of the present invention to provide dyestuffs of the said kind dyeing blue-red to yellowr'ed shades of good fastness.

It has been found that diazo dyes can be prepared if diazotised amino-azo dyes of the general formula:

wherein X represents a connecting link containing nitrogen which is different from the azo-group andR1 and R2 each represent an aryl radical, are coupled with S-hydroxyquinolines and the dyestuffs obtained treated, if desired, with agents which yield metals.

The starting products of the above formula are preferably obtained by coupling a' diazotised amine of theformula R1NH2, where R1 represents the same radical as above, with products-of the general formula in an alkaline medium. Diazotised amines of the benzene and naphthalene series (whose radical is equivalent to the R1 of the first formula) are particularly suitable. These amines may contain groups which make the substance Water-soluble, such as sulphonic acid or carboxyl groups, and other substituents. In some cases it is advisable to use amines containing a grouping which will form a metallo-complex, in particular a hydroxyl, carboxyl, or alkoxy group, or a grouping (particularly -OCH2COOH) for example in the ortho-position to the amino group to be diazotised. Suitable amines are, for example, 2- amino-1-methoxy-benzene-4 sulphonic acid, 2- amin0phenol-4 sulphonamide, anthranilic acid, 2-amino-3-naphthoic acid and 1-amino-2-methy1-5-phenoxy acetic acid. Further examples of such amines can be found in the table given later.

The linkage X of the above formula should preferably consist of at least 2 atoms, at least one of which should be nitrogen and the other one, for example, carbon. It may be, in the simplest case, an acid amine group, e. g.

This linkage, however, may also be part of a ring which acts, for example, on the ortho-a-position of the naphthalene nucleus, as is the case in the corresponding imidazoles, thiazoles or triazines.

The aryl radical R2 of the above formulas may belong, for example, to the benzene series and should preferably have the amino-group to be diazotised in the paraor meta-position to the linkage X.

The diazotisation of these amino-azo dyes having the formula given at the beginning is best undertaken in many cases indirectly by adding an acid such as hydrochloric acid at a suitable temperature to a neutral to weakly alkaline solution or suspension of the amino-azo dye containin the necessary amount of sodium nitrite or introducing the latter solution into the acid.

According to the present process this diazotised amino-azo dye, having the formula mentioned at the beginning, is combined with 8- hydroXy-quinolines. Of the latter B-hydroxyquinolines itself is primarily suitable, but substituted 8-hydroxy-quinolines such as 5-chlor- B-hydro-xy-quinoline, 8-hydroxy-quinoline-5- and 3 -7sulphonic acid and 8-hydroxy-quinolin'e-T- carboxylic acid may also be used. The coupling is carried out in an alkaline medium, which may contain, for example, alkali hydroxides such as sodium hydroxide and, if necessary, alkali carbonates.

The compounds should be chosen so that the finished dye does not contain more than 2 sul- V phonic acid groups.

The dyes obtained by the present process can be used in the usual way for dyeingrand printing the most various animal and, in particular,

'20 especially cotton, linen, rayon, and staple fibers cellulosic fibers such as wool, silk, leather and from regenerated cellulose. Predominantly bluish red to red to yellowish red shades are obtained.

Particularly valuable products are obtained if these dyes are treated in the substance, in the dye bath or on the fiber with agents which yield metals, principally copper. According to the composition of the dyes, complex metallic compounds, in particular copper compounds, are obtained, which are soluble in water and can be used for dyeing according to methods usual for directdye- Example :12

The amino azo dyestuif (obtainable in the known manner from 20.5 parts of 2-amino-lmethyl-. l-phenoxy acetic acid by diazotisation and coupling with 35.8 parts of 2-(4-aminobenzoyl) amino-5-hydroXynaphthalene-'7-sulphonic acid in sodium carbonate alkaline medium) which has been precipitated with sodium chloride, filtered and pressed, is suspended in 400 parts of water. 'Zparts-of sodium nitrite are added and the whole is cooled to 6 C. by the addition of ice. 30 parts of concentrated hydrochloric acid are then added and stirred for about 2 hours. The diazocompound obtained is now added to a solution of 14.5 parts of 8-hydr,oxyquinoline, 1.5 parts of caustic soda and 20 parts of calcined soda'in500 parts of water cooled to 4 C. After a few hours the solution is warmed to 65 C. and 100 110 200 parts of sodium chlorideare added in order to obtain an easily filterable form of the diazo dyestufi and then the solution is filtered.

and the precipitatedried. A darkbrown powder of the formula:

ing dyestuffs, or in some cases sparingly soluble to insoluble copper compounds which are best prepared on the fiber itself.

Subsequent treatment of the dyestuffs on the fiber with agents which yield metals (mainly copper) can be carried out by the usual after treatment with copper in fresh bath or with advantage in the dye bath itself after dyeing, when copper compounds which are stablev to alkalis e. g. complex copper tartrates shouldbe h used (of. U. S. Patent 2,148,659)

' Example 1 The amino azo ,dyestuif (obtainable in the known manner from 20.3 parts of 2-amino-1- inethoxy-benzene-4-su1pho nic acid by diazotisation and coupling with 35.8 parts of 2-(4'-aminobenzoyl) a mi n o-5-hydroxynaphthalene-7 s ulphonic acid in sodium carbonate alkaline medium),- which has. been precipitated with sodium chloride, filtered and pressed, is suspended in 400 parts of Water. 7 parts of sodium nitrite are added and the Whole is cooled to 6 C. ,by the addition of ice. 30 parts of concentrated hydrochloric acid are addedand stirring is carried out for about 2 hours. The diazo compound obtained is now added to a solution of -,15l.5 parts of'8- hydroxy-quinoline, 15 parts of caustic soda and 20 parts calcined soda in 500 parts of water cooled to 4? C. After a few hours the solution is warmed to 65 C. and 100 to 200 parts of sodium chloride are added in order to obtain an easily filterable form ofcthediazo dyestufi, and the solution is filtered and the precipitate dried. A dark brown powder is the result havin the formula:

NH- o 0 Omar-8.

" Hols 90H? is obtained which dissolves in water and dilute alkalies to red solutions and in concentrated sulphuricacid to a violetsolution.

Vegetable fibers and regenerated cellulose are dyed vivid yellowish red shades from neutral :or alkaline Glaubers salt bath which when after.- treated with vcupric salts become faster to light andwashing.

Example 3 a The vamino azo dyestufi. (obtainable in .the known .manner from 13.7 parts .of .2-amino-lmethoxy-A-methylbenzene .by .diazotisation and coupling with 35.8 parts of 2- (-4'.-amino-benzoyl).-,-

amino-5 hydroxynaphthalene- .7 ;.-sulphonic acid in sodium carbonate alkaline medium) which has been precipitated with sodium chloride, filtered and pressed, is dispersed in AOO-parts .of water. 7 parts of sodium nitrite are added and the whole is cooled to 6 C. with ice. 30 .parts of concentrated hydrochloric acid are then added and the whole stirred for about2 hours. The diazo compound obtained is now added to a solution of 14.5 parts of 8hydroxyquinoline, :15 parts of caustic soda and 20 parts of calcined soda in 500 parts of water cooled to 4 C. After a few hours the solution is warmed to 65 C. and 100 200 parts I of sodium chloride are added in order to obtain an easily filterableform of the disazo dyestufi and then the solution is filtered andthe precipitate dried. The result is a dark brown powder-which dissolves in water and dilute alkaliesto redsomtions and in concentrated sulphuric acid to aviolet solution. 7 7

Vegetable fibers and regenerated cellulose are dyed vivid red shades from neutral or alkaline.

Further dystufis obtained according to the present invention are given in the following Glaubers salt bath which when after-treated with cupric salts become faster to light and Washing. table:

- Shade of the Dlazo components, amino azo dyestnfi from Azo component coppeted dyeing 2-aminobenzoic acid -hydroxyquinoline Brick red.

H 033 NHC 0 NH;

2amino-R-naphthoic acid Bl uish red. 4-aminobenzoic acid Dnii red. 2 amino 1 hydroxybenzene 4 Bordeaux.

suifonamide. 2-amino-1-phenoxy-acetic acid-4- Red.

snifonamide. 2-a1nin0-4-chlor-1-phenoxy acetic Do.

ac 2 amino 6 chior 1 hydroxy Bordeaux.

bcnzene-4-sulionic acid. 2 amino -1 hydroxybenzene 4 D0.

suifonic acid. Monosulfonated 2-amino-4-ch1or- Red.

l-methoxybenzene. I 2-aminobenz0ie acid 5-chlor-S-hydroxygu1nol1ne Yeilowish red. .Z-amino-i -methoxy-4-mcthylben- 8 hyiroxyquinoline sulphonic Red.

zenc. aci

Do do 8-hygiiroxyquinoline-7-carboxylic D0.

aci 2-amino-4-chior-l-phcnoxy-acetic do 8- hygroxyquinoline 7 sulfonic Yellowish red.

acid. aci Zaminobenzoic acid 8-hydroxyqnin01ine Do.

H 0 3S NHC O 2-an1ino-3-naphthnic acid do do Bordeaux. 2-arnino-4-chlor-l-phcnoxy-acctic do .d0 Yellowish red.

aci Z-amino-l-mcthoxy-4-methy1- do .do Do.

benzene. 2-amino -1-hydroxybcnzcnc-4- do d0 Bordeaux.

suifonamide. 4-aminobenzoic acid do do Reddish orange, Z-aminobcnzoic acid do. -ch.lor-8-hydroxyqu1nohne Do. 2 amino -1 hydroxybenzene 4 do Binish red.

suliouamide. v 2-amino-l-methoxy-4-m ethylben- 8 hydroxyqumohnc 7 suifonlc Bordeaux.

zenc. acid. H 1 2-an1ino-1-methoxybenzene-4-snl- E-hydroxyquinoline I 'Do.

ionic acid.

2-amin0-1-methoxy-4-methy1bcn- Do.

zene.

i O H v v 2 aminobenzoic acid do Yeiiowish red.

' l l H OzS- NE NH:

2-amino-1-phenoxy-acetic acid Brownish red. 2 amino 4 chlor 1 hydroxy- Bordeaux. benzene- -sulfonic acid. a 4-aminobenz0ic acid Red, 4 amino 1 hydroxybenzene 2 Bi oym H -carboxylic acid.

Dlazo-component's, amino-azo-dyestufi-irom Azo-compon'ent g gzgggf ggg 2-amino-3-naphthoic acid 8-hydr0xyquinoline Bordeaux.

' I I H028 NE NH:

2-a1nino-4-chlor-l-phenoxy-acetic Bluish red.

ac: 2-amino-l-methoxybenzenei-sulf Yellowishred;

fonic acid; g Sulionated 2-amino-l-methoxy-4- Red.

methylbenzene. I Sulionated 2-amino-l-methylben- Yellowlsh red.

zene. 2-amino-l-benzoic acid. 5-chlor-8-hydroxyquinoline;- Do. I 6 -nitro -2-amino 1 -hydroxyben- .--d0 Bordeaux.

zeneA-sulfonic acid. 4-nitro-2-amino-l-hydroxybendo Do;

zene-B-sullonic acid. 2-amino-l-m ethoxyA-methylben- S hYllOXYqlllDOllDG 7 suliomc Do;v

zene. aci

Example 4 The diazo compound from 13.7 parts of 2 aminobenzoic acid is coupled at room tempera ture in the presence of an excess of sodium carbonate with 37.2 parts of 4-aminophenyl-5- hydroxy- 7 -sulpho-lzz-naphtho-thiazole. After a few hours the coupled mixture is warmed and the monoazo dyestufi is precipitated by the addition of sodium chloride and filtered. This dyestufi is dissolved in 1000 parts of wateranddiazotised at 4 C. by adding '7 parts of sodium nitrite and 35 parts of concentrated hydrochloric acid. After the diazotisation is complete, the suspension of the diazoazo compound is neutralized with soda and the solution containing 14.5 parts of 8- hydroxyquinoline in 200 parts of 10% caustic sodasolution is added. A red disazo dyestuff is formed of the formula:

V s-c- N=N- OH Hogs- N1 NzN r coon on 1 Example 5 100 parts of. cotton are entered at 40 C. into a dyebath of 3000 parts of water which contains 1 part of the dyestuff obtained accordingto Exampie 1 as well as 2 parts of sodium carbonate, and

the temperature is raised to 90 to 95 C. parts of crystallised sodium'sulphate are added and dyeing is continued for three quarters of an hour at 90 to 95 C; The'dyebath is then cooled to 70 C., the necessary quantity of a'solution ore ing carried out during half-an-hour at '70-80 C. The cotton is now thoroughly rinsed and if necessary soaped and finishedoff as usual. It is dyed red and is fast to light and washing.

What I claim is:

1. A process for the manufacture of a disazodyestufi, which comprises coupling, with an 8- hydroxyquinoline capable of coupling, a diazotized aniinoazo compound of the formula 0H wherein X stands for a link including the ar rangement consisting of oxygen and a member of a' heterocyclic ring leading to the 1-position of the naphthalene nucleus, and wherein Rrstands for an aryl radical.

2. A process for the manufacture of a disazodyestuiT, which comprises coupling, with an 8-hydroxyquinoline capable of coupling, diazotize'd aminoazo compound of the formula wherein X stands for a. link selected from the class consisting of complex copper tartrate rendered weakly alkalinewith sodium carbonate is added and copperwherein the carbon atomv is in? each case cone" nected to the phenylenev group, thebonddesignate'd'by (1) is connectejd'to the: li-positiori of the naphthalene nucleus and the bond desig-v 9 nated by (2) bein linked to the 2-position of the naphthalene nucleus, and wherein R1 stands for an aryl radical containing at least one substituent capable of promoting the formation of complex metal compounds.

3. Process for the manufacture of a disazodyestuff, which comprises coupling a diazotized aminoazo compound of the formula wherein R1 stands for an aryl radical containing at least one substituent capable of promoting the formation of complex metal compounds, with an -hydroxyquinoline capable of coupling.

4. Process for the manufacture of a disazodyestufi", which comprises coupling a diazotized aminoazo compound of the formula NHg HOaS wherein R1 stands for an aryl radical containing at least one substituent capable of promotin the formation of complex metal compounds, with an 8-hydroxyquinoline capable of coupling.

5. Process for the manufacture of a dis-azodyestuff, which comprises coupling a diazotized aminoazo compound of the formula wherein R1 stands for an aryl radical containing atleast one substituent capable of promoting the formation of complex metal compounds, with an 8-hydroxyquinoline capable of coupling.

6. A disazo-dyestuff of the formula where X stands for a, link selected from the class consisting of wherein the carbon atom is in each case connected to the phenylene group, the bond designated by (l) is connected to the 1-position of the naphthalene nucleus and the bond designated by (2) being linked to the 2-position 0f the naphthalene nucleus, R1 stands for an aryl' radical, and R3 stands for the radical of an 8-hydroxyquinoline couplin component.

8. Process for the manufacture of a disazodyestuff comprising coupling the diazotized aminoazo compound of the formula with 8-hydroxy-quinoline.

9. Process for the manufacture of a disazodyestuff comprising coupling the diazotized aminoazo compound of the formula COOH OH with S-hydroxy-quinoline. Y

10. Process for the manufacture of a disazodyestuff comprising coupling the diazotized aminoazo compound of the formula COOH with 8-hydroXy-quino1ine. 11. Disazo-dyestuffs of the general formul wherein X stands for a link containing at least one nitrogen and at least one carbon atom directly attached to each other, connecting at least one of the positions 1 and 2 of the naphthalene nucleus With'the phenylene radical, the "nitrogen being connected to the naphthalene nucleus -and the carbon atom to the phenylene radical, wherein R1 stands for an aryl radical, and R3 stands for the radical of a 8 hydroxy-quinoline coupling component.

12. Disazo-dyestuffs of the general formula wherein X stands for a link containing at least one nitrogen and carbon atom directly attached to each other, connecting at least-one of .the .positions 1 and 2 of the naphthalene nucleus With the phenylene radical, the nitrogen being connected to the naphthalene nucleus and the carbon atom to the phenylene radical, wherein R1 stands for an aryl radical containing at least one substituent capable of promoting the formation of complex metal compounds, and R3 stands for the radical of a 8-hydroxy-quinoline coupling component.

12 14. A disazo-dyestuff ofthe formula wherein R1 stands for an aryl radical containing at least one substituent capable of promoting the formation of complex metal compounds, and R3 stands for a 8-hydroxy-quinoline radical.

15. A disazo-dyestuff of the formula HOaS wherein R1 stands for an aryl radical containing at least one substituent capable of promoting the formation of complex metal compounds, and R3 stands for a 8-hydroXy-quinoline radical.

16. The disazo-dyestuff-of the formula 13. A disazo-dyestuff of the formula Holswherein R1 stands for an aryl radical containing 5 at least one substituent capable of promoting the formation of complex metal compounds, and R3 stands for a 8-hydroxy-quinoline radical.

17. The .disazo-dyestufi of the formula 18. The disazo-dyestuff of the formula H O as N WALTER ANDERAU.

OOH

Certificate of Correction Patent No. 2,411,646. November 26, 1946. WALTER ANDERAU It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 4, line 29, Example 2, for the Word diazo read disazo; column 9, line 38, claim 5, for that portion of the formula reading S C read S (J; and that the said Letters Patent should be read With these corrections therein that the same may conform to the record of the case in the Patent Ofiice.

Signed and sealed this 25th day of February, A. D. 1947.

LESLIE FRAZER,

First Assistant Commissioner of Patents. 

